US3376359A - Preparation of decatrienes - Google Patents

Preparation of decatrienes Download PDF

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Publication number
US3376359A
US3376359A US491025A US49102565A US3376359A US 3376359 A US3376359 A US 3376359A US 491025 A US491025 A US 491025A US 49102565 A US49102565 A US 49102565A US 3376359 A US3376359 A US 3376359A
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nickel
ethylene
decatriene
butadiene
reactor
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US491025A
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Schneider Wolfgang
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Covestro International SA
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BF Goodrich Corp
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Priority to US491025A priority Critical patent/US3376359A/en
Priority to NL6613476A priority patent/NL6613476A/xx
Priority to DE19661568709 priority patent/DE1568709A1/en
Priority to GB43215/66A priority patent/GB1135857A/en
Priority to FR77987A priority patent/FR1494632A/en
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Assigned to POLYSARINTERNATIONAL S.A., A CORP. OF SWITZERLAND reassignment POLYSARINTERNATIONAL S.A., A CORP. OF SWITZERLAND ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: B.F. GOODRICH COMPANY, THE
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/20—Olefin oligomerisation or telomerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/847—Nickel
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/22—Organic complexes

Definitions

  • This invention relates to a method for preparing aliphatic trienes and relates more particularly to preparation of aliphatic trienes by reacting butadiene or isoprene with ethylene in the presence of a nickel complex catalyst.
  • 1,4,9-decatriene and dimethyl-1,4,9-decatriene are useful as third monomers in introducing unsaturation in polymers of ethylene and propylene.
  • I have now found a novel and inexpensive process for preparing these trienes in good yield by reacting butadiene or isoprene with ethylene in the presence of a bisacrylonitrile nickel, bisfumaronitrile nickel, biscinnamonitrile nickel, or bisacrolein nickel catalyst.
  • This procedure otters many advantages over known methods for preparing these aliphatic trienes.
  • the catalyst is inexpensive, does not have to be prepared in situ, can be prepared in advance and stored, and the resulting catalyst reaction product does not contain undesirable impurities which are often found in other catalysts.
  • the catalysts are readily prepared by refluxing nickel tetracarbonyl with a compound containing activated double bonds as fumaronitrile, cinnamonitrile, acrolein or acrylonitrile, under nitrogen, and isolating the crystalline nickel complex formed by filtration.
  • the catalyst may be suspended in dry, oxygenfree butadiene or isoprene and ethylene added in an autoclave.
  • the temperature of the reaction may be between 25 to 250 C. and preferably is between 50 to 150 C.
  • the reaction is conducted under sufficient pressure to dissolve ethylene in the butadiene or isoprene at the temperature of the reaction.
  • the pressure may vary from about 100 p.s.i. to 5000 p.s.i.
  • the amount of catalyst used varies from as low as to 5% or more but large amounts of catalysts are not required.
  • An amount of catalyst from about 10- to 2% based on the amount of butadiene or isoprene and ethylene used is sufiicient. While solvents may be used they are not necessary.
  • the following examples demonstrate methods for preparing 1,4,9-decatrienes in accordance with this invention.
  • Example I 0.85 gram of bisacrylonitrile nickel was added to a 320 ml. autoclave containing 120 grams of dry, oxygenfree butadiene-1,3. 50 grams of ethylene was added to the reactor at room temperature and the reactor heated to 80 C. for 45 hours. At the end of this period the reactor was vented and the reaction product was found to Patented Apr. 2, 1968 contain 51.5% of 1,4,9-decatriene at a conversion of 98% which is readily purified by distillation to a purity of 99.+%, and about 15% cyclodecadiene.
  • Example II 1.2 gram of bisacrolein nickel was added to a 320 ml. autoclave containing 98 grams of dry, oxygen-free butadiene-1,4. 47 grams of ethylene was charged to the reactor .and the reactor heated to C. for 45 hours. At the end of this period the reactor was vented and the reaction product was found to contain 27% of 1,4,9-decatriene at a conversion of Example IV 0.8 gram of bisfumaronitrile nickel was added to a 320 ml. autoclave containing grams of dry, oxygenfree butadiene-1,3. 58 grams of ethylene was added to the reactor at room temperature and the reactor heated to 80 C. for 60 hours. At the end of this period the reactor was vented and the reaction product was found to contain 19.5% of 1,4,9-decatriene.
  • Example V 0.3 gram of bisfumarom'trile nickel was added to a 320 ml. autoclave containing 128 grams of dry, oxygen-free isoprene. 42 grams of ethylene was added to the reactor at room temperature and the reactor heated to 80 C. for 60 hours. At the end of this period the reactor was vented and the reaction product was found to contain 67.3% of dimethyl 1,4,9-decatrienes.
  • the dimethyl-1,4,9-decatriene contained a mixture of 52.1% of 5,8 dimethyl 1,4,9- decatriene and 4,8 dimethyl 1,4,9-decatriene and 15.2% of 4,9 dimethyl 1,4,9 decat-riene and 5,9-dimethyl- 1,4,9-decatriene.
  • a method for preparing decatrienes which comprises reacting a compound selected from the group consisting of butadiene and isoprene with ethylene in the presence of catalytic amounts of a nickel compound selected from the group consisting of bisacrylonit-rile nickel, bisfumaronitrile nickel, biscinnamonitrile nickel and bisacrolein nickel.
  • a method for preparing 1,4,9-decatriene which comprises reacting butadiene and ethylene at an elevated temperature in the presence of catalytic amounts of a nickel compound selected from the group consisting of bisacrylonitrile nickel, bisfumaronitrile nickel, biscinnamonitrile nickel and bisacrolein nickel.
  • a method for preparing dimethyl-l,4,9-decatrienes which comprises reacting isoprene with ethylene at an elevated temperature in the presence of catalytic amounts of a nickel compound selected from the group consisting 4 of bisacrylonitrile nickel, bisfurnaronitrile nickel, biscin- References Cited namonitrile nickel and bisacrolein nickel.
  • a nickel compound selected from the group consisting 4 of bisacrylonitrile nickel, bisfurnaronitrile nickel, biscin- References Cited namonitrile nickel and bisacrolein nickel.
  • UNITED STATES PATENTS 4.
  • a th df 1,4,9-dec tri ne h h omme 0 Orprepanng a e w c 2,972,640 3/1961 Burks 260666 prises reacting butadiene with ethylene at a temperature between about 50 to 150 C. under pressure in the pres- FOREIGN PATENTS ence of about 10* to
  • a method for preparing dimethyl-l,4,9-decatriene 1043143 7/1963 which comprises reacting isoprene with ethylene at a temperature between about 50 to 150 C. under pressure D ELBERT GANTZ Primary Examiner in the presence of about 10- to 2% bisacrylonitrile 10 J. D, M S Assistant Examineh nickel.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Description

United States Patent 3,376,359 PREPARATION OF DECATRIENES Wolfgang Schneider, Broadview Heights, Ohio, assignor to The B. F. Goodrich Company, New York, N.Y., a corporation of New York No Drawing. Filed Sept. 28, 1965, Ser. No. 491,025 5 Claims. (Cl. 260-677) ABSTRACT (IF THE DISCLOSURE Aliphatic trienes, 1,4,9-decatriene and dimentyl-l,4,9- decatriene, are prepared by reacting ethylene with butadiene or isoprene in the presence of a bisacrylonitrile nickel, bisfumaronitrile nickel, biscinnamonitrile nickel or bisacrolein nickel catalyst. These trienes are useful as third monomers to introduce unsaturation into polymers of ethylene and propylene.
This invention relates to a method for preparing aliphatic trienes and relates more particularly to preparation of aliphatic trienes by reacting butadiene or isoprene with ethylene in the presence of a nickel complex catalyst.
1,4,9-decatriene and dimethyl-1,4,9-decatriene are useful as third monomers in introducing unsaturation in polymers of ethylene and propylene. I have now found a novel and inexpensive process for preparing these trienes in good yield by reacting butadiene or isoprene with ethylene in the presence of a bisacrylonitrile nickel, bisfumaronitrile nickel, biscinnamonitrile nickel, or bisacrolein nickel catalyst. This procedure otters many advantages over known methods for preparing these aliphatic trienes. In addition to good yields, the catalyst is inexpensive, does not have to be prepared in situ, can be prepared in advance and stored, and the resulting catalyst reaction product does not contain undesirable impurities which are often found in other catalysts.
The catalysts are readily prepared by refluxing nickel tetracarbonyl with a compound containing activated double bonds as fumaronitrile, cinnamonitrile, acrolein or acrylonitrile, under nitrogen, and isolating the crystalline nickel complex formed by filtration.
In preparing 1,4,9 decatriene and dimethyl 1,4,9- decatriene the catalyst may be suspended in dry, oxygenfree butadiene or isoprene and ethylene added in an autoclave. The temperature of the reaction may be between 25 to 250 C. and preferably is between 50 to 150 C. The reaction is conducted under sufficient pressure to dissolve ethylene in the butadiene or isoprene at the temperature of the reaction. The pressure may vary from about 100 p.s.i. to 5000 p.s.i. The amount of catalyst used varies from as low as to 5% or more but large amounts of catalysts are not required. An amount of catalyst from about 10- to 2% based on the amount of butadiene or isoprene and ethylene used is sufiicient. While solvents may be used they are not necessary. The following examples demonstrate methods for preparing 1,4,9-decatrienes in accordance with this invention.
Example I 0.85 gram of bisacrylonitrile nickel was added to a 320 ml. autoclave containing 120 grams of dry, oxygenfree butadiene-1,3. 50 grams of ethylene was added to the reactor at room temperature and the reactor heated to 80 C. for 45 hours. At the end of this period the reactor was vented and the reaction product was found to Patented Apr. 2, 1968 contain 51.5% of 1,4,9-decatriene at a conversion of 98% which is readily purified by distillation to a purity of 99.+%, and about 15% cyclodecadiene.
Example II Example III 1.2 gram of bisacrolein nickel was added to a 320 ml. autoclave containing 98 grams of dry, oxygen-free butadiene-1,4. 47 grams of ethylene was charged to the reactor .and the reactor heated to C. for 45 hours. At the end of this period the reactor was vented and the reaction product was found to contain 27% of 1,4,9-decatriene at a conversion of Example IV 0.8 gram of bisfumaronitrile nickel was added to a 320 ml. autoclave containing grams of dry, oxygenfree butadiene-1,3. 58 grams of ethylene was added to the reactor at room temperature and the reactor heated to 80 C. for 60 hours. At the end of this period the reactor was vented and the reaction product was found to contain 19.5% of 1,4,9-decatriene.
Example V 0.3 gram of bisfumarom'trile nickel was added to a 320 ml. autoclave containing 128 grams of dry, oxygen-free isoprene. 42 grams of ethylene was added to the reactor at room temperature and the reactor heated to 80 C. for 60 hours. At the end of this period the reactor was vented and the reaction product was found to contain 67.3% of dimethyl 1,4,9-decatrienes. The dimethyl-1,4,9-decatriene contained a mixture of 52.1% of 5,8 dimethyl 1,4,9- decatriene and 4,8 dimethyl 1,4,9-decatriene and 15.2% of 4,9 dimethyl 1,4,9 decat-riene and 5,9-dimethyl- 1,4,9-decatriene.
I claim:
1. A method for preparing decatrienes which comprises reacting a compound selected from the group consisting of butadiene and isoprene with ethylene in the presence of catalytic amounts of a nickel compound selected from the group consisting of bisacrylonit-rile nickel, bisfumaronitrile nickel, biscinnamonitrile nickel and bisacrolein nickel.
2. A method for preparing 1,4,9-decatriene which comprises reacting butadiene and ethylene at an elevated temperature in the presence of catalytic amounts of a nickel compound selected from the group consisting of bisacrylonitrile nickel, bisfumaronitrile nickel, biscinnamonitrile nickel and bisacrolein nickel.
3. A method for preparing dimethyl-l,4,9-decatrienes which comprises reacting isoprene with ethylene at an elevated temperature in the presence of catalytic amounts of a nickel compound selected from the group consisting 4 of bisacrylonitrile nickel, bisfurnaronitrile nickel, biscin- References Cited namonitrile nickel and bisacrolein nickel. UNITED STATES PATENTS 4. A th df 1,4,9-dec tri ne h h omme 0 Orprepanng a e w c 2,972,640 3/1961 Burks 260666 prises reacting butadiene with ethylene at a temperature between about 50 to 150 C. under pressure in the pres- FOREIGN PATENTS ence of about 10* to 2% bisacrylonitrile nickel.
5. A method for preparing dimethyl-l,4,9-decatriene 1043143 7/1963 Great Bntam' which comprises reacting isoprene with ethylene at a temperature between about 50 to 150 C. under pressure D ELBERT GANTZ Primary Examiner in the presence of about 10- to 2% bisacrylonitrile 10 J. D, M S Assistant Examineh nickel.
US491025A 1965-09-28 1965-09-28 Preparation of decatrienes Expired - Lifetime US3376359A (en)

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US491025A US3376359A (en) 1965-09-28 1965-09-28 Preparation of decatrienes
NL6613476A NL6613476A (en) 1965-09-28 1966-09-23
DE19661568709 DE1568709A1 (en) 1965-09-28 1966-09-27 Process for the production of decatrienes
GB43215/66A GB1135857A (en) 1965-09-28 1966-09-28 Decatrienes
FR77987A FR1494632A (en) 1965-09-28 1966-09-28 Process for the preparation of decatrienes

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3726935A (en) * 1972-05-05 1973-04-10 Du Pont Preparation of 1,6,8-decatriene

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2972640A (en) * 1959-04-27 1961-02-21 Cities Service Res & Dev Co Cycloolefin production utilizing isobutylene or its dimerization product as catalyst activator
GB1043143A (en) * 1962-07-28 1966-09-21 Basf Ag Production of open chain oligomers of 1,3-dienes

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2972640A (en) * 1959-04-27 1961-02-21 Cities Service Res & Dev Co Cycloolefin production utilizing isobutylene or its dimerization product as catalyst activator
GB1043143A (en) * 1962-07-28 1966-09-21 Basf Ag Production of open chain oligomers of 1,3-dienes

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3726935A (en) * 1972-05-05 1973-04-10 Du Pont Preparation of 1,6,8-decatriene

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GB1135857A (en) 1968-12-04
NL6613476A (en) 1967-03-29
DE1568709A1 (en) 1970-03-26

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